Photopolymerization process and compositions



Patented June 9, 1953 UNITED STATES PATE'NT- {OFFICE PHOTOPOLYMERIZ ATION PROCESS AND COMPOSITIONS Carrol C. Sachs, North Hollywood, and John Bond,Los Angeles, .Calif., assignors to Alexander H. Kerr and Company, Incorporated, Los Angeles, Calif., a corporation of'Nevada N Drawing. Application November 6, 1948,

Serial No. 58,814

The photochemical polymerization of ethylenically unsaturated monomers and low molecular.

weight polymers of such unsaturated monomers has been described in the prior art.

This invention relates'tothe discovery that halogenated mono ketaldonyl compounds are highly efiicient photopolymerization catalysts for the ethylenically unsaturated resinophors.

It is generally well known that certain of the organic resinophoric' compounds are light-sensitive in that light reduces the induction period or increases the rate of olymerization. Such compounds are those resinophoric compounds which contain radicals which include an ethylene linkage and which polymerize according to the vinyl type of polymerization. Such compounds have been classed as vinyl types (see Plastics, Resins". and Rubber, by Paul 0. Powers, Chemical and" Engineering News, October 25, 1946-, vol 24, No.

200, page 2784).

These include the acrylic resins, i.- e, resins produced by polymerization of acrylic acid' or derivatives ofacrylic acid, for example, methyl, acrylic acid, or methyL-ethyl, butyl' acrylatey' methyl methacrylate, ethyl methacrylate butyl methacrylate, isobutyl methacrylate. Such types .i also include styrene and its derivatives, for example, styrene and the alkyl nuclear substituted styrenes, such as ortho or metamethyl styrene or the chlorinated styrenes. It also includes chloroprene. This type also includes the allyl compounds, such as allyl alcohol and allyl alcohol condensed with poly basic acids, as in 'allyl maleate or allyl phthalate or the condensate of allyl-" alcohol with .poly basic acids and polyhydric al- -Such types also include vinyl acetate, vinyl;

halides, for example, vinyl chloride and vinylidene' cohols to form suitable copolymers. i

halides, for example, vinylidene chloride.

Th addition of a small amount of the photopolymerization catalyst of our invention to. the photopolymerizable monomers or partial poly- 11 Claims. 01. 204-158) mers positively catalyzes the .photopolymerization materially.

These catalysts are also active for mixed monomers or mixed partial polymers or for the poly-.

merization-of mixed monomers or mixed partial polymers capable of copolymerization. I Our cata-" lysts catalyze the photopolymerization'of copolymers of esters of'unsaturated glycols such'as ethene or butene diols and unsaturated dicarboxylic acids, such as maleic, fumeric or itaconic acid, or copolymers thereof with the above vinyl type of 'resinophoric compounds, as, for example, 1

vinyl acetate orstyr 2 Thus, these catalysts are active in the photopolymerization of the allyl esters and particularly the allyl esters of the polycarboxylic acid, such;

as diallyl maleate or diallyl vphthalate and their copolymers with the above vinyl type resinophors,

Polyglycol' esters of acrylic and methacrylic esters and their copolymers with the resinophors of the vinyl type as stated above are also included.

Cross linking agents may be employed which contain two or more terminal ethylene linkages (CH2:C which may enter into a vinyl type of polymerization. These include ethylene dimethacrylate; allyl methacrylate; methacrylate; ethylene glycol dimethacrylate; hexamethyleng glycol dimethacrylate; dimethallyl carbonate; and similar compounds.

All of the above resinophoric compounds contain C:C' (ethylenic) linkages in resinophoric arrangement. As stated above, certain of them are of the vinyl type and others, particularly certain of the ester types, are not all strictly classifiable as vinyl type polymers, in that their polymerization is not strictly of the vinyl type, since cross linkage to form three-dimensional resinsis also possible. These may be classed as the non-vinyl ester type resinophors. They are all classifiable as' ethylenically unsaturated resinophors and since, especially when catalyzed by our catalysts, they are photochemically polymerizable, they may thusbe classed as ethylenically unsaturated photochemically polymerizable whereR is selected .from the group consisting of halogen atoms and'm'onovalent hydrocarbon groups consisting solely of hydrogen and carbon atoms, X is ahalogen atom, .X; is selected from the group, consisting of halogen atoms and hydrogen atoms, and R1 is selected from the group consisting of hydrogen atoms and monovalent hydrocarbon groups consisting solely of hydrogen and carbon atoms.

Examples of'the mono ketaldonyl photochemical catalyst of our invention are the halogenated compounds such as desyl halides, 'forexample,

desyl chloride and bromide, and halogenated methallyl aldehydes such as beta dichlor propionaldehyde or alpha beta di-brompropionaldehyde, chloral, and bromal. These examples are given only by way of example to illustrate the generic invention of the suitability of the halogenated ketaldonyls as described above and the specific utility ofthe chlorinated aldehydes and the chlorinated ketonic compounds stated generically and specifite cally above.

We may incorporate a small amount of; the.

catalyst up to about 5% of the weight of the monomer or partial polymer to which it, isadded'.

It is possible to add too much of. the catalystand thus impair its activity. The amount will; vary with the resinophor and the catalyst and the simple tests explained below will permit .O'f. the choosing of the optimum concentration of cata: lyst.

EXAMPLE 1 The comparative value of the. chlerinated,

mono ketaldonyl to the corresponding hydroxe ylated compound is shown by the. cmparative activity of chloral and chloralhydrate,

A one per cent solution of chloral hydrate was made in methyl methacrylatemonomer. Alike per cent solution of chloral'was made in methyl methacrylate which was rigorously dried by shaking with a desiccant. Each of thesolutions was.

poured into like Pyrex vials of equal height and diameter and filled to a like level and exposed side by side to sunlight. Periodically, samples were simultaneously withdrawn from each of the flasks and analyzedby dissolving the sam les.

in methanol. Theprecipitated polymer was dried and weighed.

Table 1- Percent Percent Elapsed Time, Minutes Polymer j 3%??? Ohloral v Hydrate po yme- A blank sample also. exposed in the same man; ner gave no perceptible polymerization.

The above experiment shows the aQtiVity of the chloral. It will be observed that. the chloral.

is much more active than the chloral hydrate. In other words, the aldehyde group was more active than the alcohol-group.

EXAMPLE 2 This example illustrates the activity. of. the. desyl halide species of our. photopolymerization.

catalysts.

One per cent solution in methylmethacrylate of desyl chloride and uncatalyzed methyl methe acrylate was placed in a Pyrex vial andexposed to sunlight. Samples were taken. at different times from the vial. These samples. were dis-. solved in methanol and the precipitated polymer filtered, dried, and weighed. The following table gives the per cent by weight of. the. precipitated,

polymer.

Table 2 Percent Elapsed Time of Exposure, Minutes precipitated 5 polymer The uncatalyzed monomer showed no perceptible polym atio EXAMPLE 3 PercentaPolymenqiten- Compound 15 .30 48 -120v 'm mfn min. 60mm 0" indicates no polymer precipitate.

It: will be observed that. thehalogenated. compound: is more active than its. analogue. Come. pare desylchloride (CsHsCOCHClCsHs) anddesyl bromide (C6H5COCHB1C6H5) withdesoxybenzoin.

The. brom compound ape- (.CeHsCOCI-IzGeI-IS) pears more active than the corresponding chloride. chloride with desyl bromide.

The efiect otconcentrationon activity 181111159 trated by the following example:

r s n emp oyed was a mixture c. r.-1rmno-. m rit st rene andanolymer or-maleic anhydride The following resin mixtures a ni th t bula ed. percent desyl;

nd. a p y th l ne ly e h ori e wer po d to. sun ht side by. side with, the following results;

0 1 a e of in cite!- Percent Catalyst 10 min 20 min. 225 min.

stifi ge 1 cured; do-.- Do,v

do Do., gel D0; Bu m se-.- su ted- 1 eno re soft cu Similar results are obtainable. when. using the other; resinophors referred to.

The previous-5 examples. indicate. the utility-of. th -phe po ym iz on catalysts of our inven-- on in e pho oe ym rizat n of o o ers and partial polymers according to these-called.

Compare chloral with. bromal. and. desyl bulk method. In such methods the. catalyst; in the desired percentage is dissolved monomers or partially bulked or polymerized monomers of suificiently low viscosity to permit of the incorporation of the catalyst. The resinophoric compound containing the catalyst may be polymerized photochemically by exposing the same to a source of ultra-violet or visible light. Temperature control to prevent excessive generation of heat during polymerization is desirable. The illuminationmay be by a light source positioned above the exposed surface of the container or where the container is light-transmitting, as when it is of glass, it may be made from a light source through the glass vessel. There are now available ultra-violet light sources which may be suspended inside the reaction vessel and these may be conveniently used.

Thevessel may be of the desired shape to form a mold to give a molded casting of desired shape. Photochemical laminations may also, be made as when the sheets being laminated are light-transmitting as, for example, if they be made of fibre glass, glass sheets, or plastic mesh or plastic sheets. In such cases the laminate, especially when the resin employed is of the contact type, may be formed into the desired laminate of the desired shape and set by photochemical means, as by exposing the laminate to sunlight or to a special source of illumination as indicated above.

The casting of thelaminate may be further baked if further hardening or polymerization of the photopolymerized product is desired. The photopolymerization process may be carried out at low or at elevated temperatures but as the temperatures become high, bubbles and striations may be formed in the castings. Since the catalyzed photopolymerization permits of rapid polymerization at low temperatures to produce bubble free castings, it is usually preferable to cause the reaction to occur at ordinary atmospheric temperatures and, if desired, even at low temperatures, i. e., at temperatures ranging from 5 to 50 C. These temperature limits are not critical and merely indicate that heat is not necessary to cause the reaction to proceed.

However, since thermal polymerization is not inhibited by these catalysts and may also be carried out simultaneously, elevated temperatures are not a hindrance so long as they are not so high as to cause bubbles or other defects, as will be recognized by those skilled in the art.

Photopolymerization employing our catalyst may also 'be carried out in a solution of the monomer or partial polymer in a volatile solvent. Thus, the monomer or partial polymer containing the catalyst is dissolved in a solvent and introduced into a vessel and illuminated. Usual precautions against the loss of solvent and cooling, where necessary to avoid overheating, may be employed. The solution is illuminated in a manner similar to that described above for bulk polymerization. Instead of polymerizing a bulk quantity solution in a vessel, we may saturate a sheet or a plurality of sheets arranged in laminated form with such solution and photopolymerize in a manner similar to that described above. The solvent may be evaporated either during, prior to, or subsequent to the photopolymerization.

We may, if desired, add conventional thermal polymerization catalysts, such as the peroxide catalysts like benzoyl, lauroyl, tertiary butyl hydrogen peroxide in addition to the photopolymerization catalyst. Thus, photopolymerization may-"be carried on either at low or-at elevated temperatures and the photopolymerized gel may be hardened further byheating the photochemically gelled product. 3 This permits of a relatively low temperature setting of the resinto .pre-bodied form or to a relatively hard castingwhich may then be baked at an elevated temperature. This is equallytrue when laminating. Thus, the laminate maybe set at relatively low tem-, perature by photopolymerization and the laminating bondhardened 'by baking.

By this process not only is the clearness and the integrity of the hardened gell increased, but the photopolymerization step accelerates the total time of cure. The rate of photopolymerization may also be increased by suitable concentrations of the catalyst as indicated above; I

When oxygen is found to deleteriously affect the rate of polymerization; vessels containing the material undergoing photopolymerization may 'be evacuated or an inert gaseous-atmosphere, as, for instance, a nitrogen atmosphere, may be employed.

It'will be understood by those skilled in the art that variousplasticizers,modifying agents such as modifying resins, fillers, etc, as isxcone. ventional in this art, may also beincorporated in the compositions described above.

The above descriptionand examples are intended to be illustrative only. Any modification of andvariation therefrom which-.conformsto the spirit ofv the invention is intendedtobe'included within the scope of the claims. 7 This application isla, continuation-in-part of Serial No. 717,796 now United States Patent 2,548,685 issued April 10,195.1.-

We claim: r I

1. As a composition of matter, a catalyzed photopolymerizable resinophor compositioncon: sisting essentially of an ethylenically unsaturated resinophor containing dispersed therein a minor proportion of a halogenated mono ketaldonyl having the formula:

MLLR.

where R is selected from the group consisting of halogen atoms and monovalent hydrocarbon groups consisting solely of hydrogen and carbon atoms, X is a halogen atom, X1 is selected from the group consisting of halogen atoms and hydrogen atoms, and R1 is selected from the group consisting of hydrogen atoms and monovalent hydrocarbon groups consisting solely of hydrogen and carbon atoms.

2. As a composition of matter, a catalyzed photopolymerizable resinophor composition consisting essentially of an ethylenically unsaturated resinophor containing dispersed therein from about 0.1 per cent to about 5 per cent of a halogenated mono! ketaldonyl having the formula:

where R is selected from the group consisting of halogen atoms and monovalent hydrocarbon groups consisting solely of hydrogen and carbon atoms, X is a halogen atom, X1 is selected from the group consisting of halogen atoms and hydrogen atoms, and R1 is selected from the group consisting of hydrogen atoms and monovalent 

1. AS A COMPOSITION OF MATTER, A CATALYZED PHOTOPOLYMERIZABLE RESINOPHOR COMPOSITION CONSISTING ESSENTIALLY OF AN ETHYLENICALLY UNSATURATED RESINOPHOR CONTAINING DISPERSED THEREIN A MINOR PROPORTION OF A HALOGENATED MONO KETALDONYL HAVING THE FORMULA: 